Method of manufacturing semiconductor device, method of processing substrate, substrate processing apparatus and computer-readable recording medium

ABSTRACT

A method of manufacturing a semiconductor device, includes: alternately performing (i) a first step of alternately supplying a first raw material containing a first metal element and a halogen element and a second raw material containing a second metal element and carbon to a substrate by a first predetermined number of times, and (ii) a second step of supplying a nitridation raw material to the substrate, by a second predetermined number of times, wherein alternating the first and second steps forms a metal carbonitride film containing the first metal element having a predetermined thickness on the substrate.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.14/668,725, filed on Mar. 25, 2015, which is a continuation of U.S.patent application Ser. No. 14/190,574, filed on Feb. 26, 2014, which isa continuation of U.S. patent application Ser. No. 13/616,148, filed onSep. 14, 2012, which issued as U.S. Pat. No. 8,951,912 on Feb. 10, 2015,which is based upon and claims the benefit of priority from JapanesePatent Application No. 2011-200292, filed on Sep. 14, 2011, and JapanesePatent Application No. 2012-139741, filed on Jun. 21, 2012, the entirecontents of which are incorporated herein by reference

TECHNICAL FIELD

The present disclosure relates to a semiconductor device manufacturingmethod including a process of forming a thin film on a substrate, asubstrate processing method, a substrate processing apparatus and acomputer-readable recording medium for storing instructions thereof.

BACKGROUND

With high integration and high performance of semiconductor devices suchas MOSFETs (Metal-Oxide-Semiconductor Field Effect Transistors) and thelike, various kinds of metal films are being used for electrodes,wirings and so on. For example, a metal carbide film such as a tantalumcarbide (TaC) film, a titanium carbide (TiC) film or the like may beused for a gate electrode of a MOSFET from the standpoint of oxidationresistance, electric resistivity, work function and so on.

In consideration of film formation of a three-dimensional structurerequiring step coverage, the above-mentioned metal carbide film may beformed using a CVD (Chemical Vapor Deposition) method rather than adeposition method such as sputtering. However, it has been difficult inthe past to form a metal carbide film using the CVD method. Indeed,although many examples of forming metal nitride films using the CVDmethod has been reported, examples of forming metal carbide films havenot been reported.

SUMMARY

The present disclosure provides some embodiments of a semiconductordevice manufacturing method, a substrate processing method, a substrateprocessing apparatus and a computer-readable recording medium storingthe instructions for executing such processes, which are capable offorming a metal carbide film that achieves good step coverage.

According to some embodiments, there is provided a method ofmanufacturing a semiconductor device, including: alternately performing(i) a first step of alternately supplying a first raw materialcontaining a first metal element and a halogen element and a second rawmaterial containing a second metal element and carbon to a substrate bya first predetermined number of times, and (ii) a second step ofsupplying a nitridation raw material to the substrate by a secondpredetermined number of times, wherein alternating the first and secondsteps forms a metal carbonitride film containing the first metal elementhaving a predetermined thickness on the substrate.

According to some other embodiments, there is provided is a method ofprocessing a substrate, including: alternately performing (i) a firststep of alternately supplying a first raw material containing a firstmetal element and a halogen element and a second raw material containinga second metal element and carbon to a substrate by a firstpredetermined number of times, and (ii) a second step of supplying anitridation raw material to the substrate by a second predeterminednumber of times, wherein alternating the first and second steps forms ametal carbonitride film containing the first metal element having apredetermined thickness on the substrate.

According to some other embodiments, there is provided an apparatus forprocessing a substrate, including: a process chamber configured toaccommodate a substrate; a first raw material supply system configuredto supply a first raw material containing a first metal element and ahalogen element to the substrate in the process chamber; a second rawmaterial supply system configured to supply a second raw materialcontaining a second metal element and carbon to the substrate in theprocess chamber; a nitridation raw material supply system configured tosupply a nitridation raw material to the substrate in the processchamber; and a control unit configured to control the first raw materialsupply system, the second raw material supply system and the nitridationraw material supply system so as to alternately perform (i) a first stepof alternately supplying the first raw material and the second rawmaterial to the substrate in the process chamber by a firstpredetermined number of times, and (ii) a second step of supplying thenitridation raw material to the substrate in the process chamber by asecond predetermined number of times, wherein alternating the first andsecond steps forms a metal carbonitride film containing the first metalelement having a predetermined thickness on the substrate.

According to yet other embodiments, there is provided acomputer-readable recording medium for storing a program that causes acomputer to perform a process including: alternately performing (i) afirst step of alternately supplying a first raw material containing afirst metal element and a halogen element and a second raw materialcontaining a second metal element and carbon to a substrate in a processchamber of a substrate processing apparatus by a first predeterminednumber of times, and (ii) a second step of supplying a nitridation rawmaterial to the substrate in the process chamber, by the secondpredetermined number of times, wherein alternating the first and secondsteps forms a metal carbonitride film containing the first metal elementhaving a predetermined thickness on the substrate.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic view illustrating a configuration of a verticaltreatment furnace of a substrate processing apparatus, in which aportion of the treatment furnace is shown by a longitudinal sectionalview, according to some embodiments.

FIG. 2 is a schematic view illustrating a configuration of the verticaltreatment furnace of the substrate processing apparatus, in which aportion of the treatment furnace is shown by a sectional view takenalong line A-A in FIG. 1.

FIG. 3 is a schematic view illustrating a configuration of a controllerof the substrate processing apparatus, according to some embodiments.

FIG. 4 is a view illustrating a flow of film formation in a firstsequence according to some embodiments.

FIG. 5 is a view illustrating a flow of film formation in a secondsequence according to some embodiments.

FIG. 6 is a view illustrating timings of gas supply in the firstsequence according to some embodiments.

FIG. 7 is a view illustrating timings of gas supply in the secondsequence according to some embodiments.

FIG. 8 is a view illustrating a flow of film formation in a firstexample, according to some embodiments.

FIG. 9 is a view illustrating timings of gas supply in a first example,according to some embodiments.

FIGS. 10A to 10C are views illustrating results of measurement of an XRFspectrum in a first example, according to some embodiments.

FIG. 11 is a view illustrating timings of gas supply in a secondexample, according to some embodiments.

FIG. 12 is a view illustrating timings of gas supply in a secondexample, according to some embodiments.

FIGS. 13A and 13B are views illustrating results of measurement of anXRF spectrum in a second example, according to some embodiments.

DETAILED DESCRIPTION

Various embodiments will be now described with reference to thedrawings.

(1) Configuration of Substrate Processing Apparatus

FIG. 1 is a schematic view illustrating a configuration of a verticaltreatment furnace 202 of a substrate processing apparatus, according tosome embodiments, in which a portion of the treatment furnace is shownby a longitudinal sectional view. FIG. 2 is a schematic viewillustrating a configuration of the vertical treatment furnace 202 ofthe substrate processing apparatus, according to some embodiments, inwhich a portion of the treatment furnace is shown by a sectional viewtaken along line A-A in FIG. 1. The present disclosure is not limited tothe substrate processing apparatus according to these embodiments, butmay be applied to other substrate processing apparatus having atreatment furnace of single wafer type, hot wall type, cold wall type,or the like.

As shown in FIG. 1, the vertical treatment furnace 202 has a heater 207as a heating means (heating mechanism). The heater 207 has a cylindricalshape and is supported by a heater base (not shown) as a support plateso as to be vertically arranged. The heater 207 acts as an activationmechanism to activate gas with heat, as will be described later.

A reaction tube 203 forming a reaction vessel (process vessel) isdisposed inside the heater 207 in a concentric form along the heater207. The reaction tube 203 is made of a heat resistant material such as,for example, quartz (SiO₂), silicon carbide (SiC) or the like and has acylindrical shape with its upper end closed and its lower end opened. Aprocess chamber 201 is formed in a hollow of the reaction tube 203 andis configured to accommodate wafers 200. The wafers 200 are horizontallystacked in multiple stages to be aligned in a vertical direction in aboat 217 which will be described later.

A first nozzle 249 a as a first gas introduction part, a second nozzle249 b as a second gas introduction part, and a third nozzle 249 c as athird gas introduction part are disposed to penetrate through a lowerside wall of the reaction tube 203. The first nozzle 249 a, the secondnozzle 249 b and the third nozzle 249 c are respectively connected to afirst gas supply pipe 232 a, a second gas supply pipe 232 b and a thirdgas supply pipe 232 c. In this way, the three nozzles 249 a, 249 b and249 c and the three gas supply pipes 232 a, 232 b and 232 c are providedin the reaction tube 203 to allow several kinds of (3 in this example)gases to be supplied into the process chamber 201.

An exhaustion pipe 231 is disposed at a lower portion of the reactiontube 203. In addition, a metal manifold (not shown) to support thereaction tube 203 may be disposed below the reaction tube 203 and thenozzles 249 a, 249 b and 249 c may be disposed to penetrate through aside wall of the metal manifold. In this case, the exhaustion pipe 231may be disposed at the metal manifold, rather than the lower portion ofthe reaction tube 203.

A mass flow controller (MFC) 241 a as a flow rate controller (a flowrate control unit) and an opening/closing valve 243 a are disposed inthe first gas supply pipe 232 a in this order from the upstreamdirection. In addition, a first inert gas supply pipe 232 d is connectedto the downstream side of the valve 243 a of the first gas supply pipe232 a. A mass flow controller (MFC) 241 d as a flow rate controller (aflow rate control unit) and an opening/closing valve 243 d are disposedin the first inert gas supply pipe 232 d in this order from the upstreamdirection. In addition, the above-mentioned first nozzle 249 a isconnected to a leading end of the first gas supply pipe 232 a. The firstnozzle 249 a is vertically disposed along the inner wall of the reactiontube 203 in a circular arc-shaped space between the inner wall of thereaction tube 203 and the wafers 200. The first nozzle 249 a is disposedin the flank of a wafer arrangement region where the wafers 200 arearranged and horizontally surrounds the wafer arrangement region. Thefirst nozzle 249 a is configured as an L-like long nozzle and has itshorizontal portion disposed to penetrate through the lower side wall ofthe reaction tube 203 and its vertical portion disposed to rise from atleast one end of the wafer arrangement region toward the other endthereof. A plurality of gas supply holes 250 a through which gas issupplied is disposed at a side surface of the first nozzle 249 a. Thegas supply holes 250 a are opened toward the center of the reaction tube203 to supply gas toward the wafers 200. The gas supply holes 250 a aredisposed to span from the bottom to top of the reaction tube 203 at apredetermined opening pitch. Each of the gas supply holes 250 a have thesame opening area. A first gas supply system is mainly constituted bythe first gas supply pipe 232 a, the mass flow controller 241 a, thevalve 243 a and the first nozzle 249 a. In addition, a first inert gassupply system is mainly constituted by the first inert gas supply pipe232 d, the mass flow controller 241 d and the valve 243 d.

A mass flow controller (MFC) 241 b as a flow rate controller (a flowrate control unit) and an opening/closing valve 243 b are disposed inthe second gas supply pipe 232 b in this order from the upstreamdirection. In addition, a second inert gas supply pipe 232 e isconnected to the downstream side of the valve 243 b of the second gassupply pipe 232 b. A mass flow controller (MFC) 241 e as a flow ratecontroller (a flow rate control unit) and an opening/closing valve 243 eare disposed in the second inert gas supply pipe 232 e in this orderfrom the upstream direction. In addition, the above-mentioned secondnozzle 249 b is connected to a leading end of the second gas supply pipe232 b. The second nozzle 249 b is vertically disposed along the innerwall of the reaction tube 203 in a circular arc-shaped space between theinner wall of the reaction tube 203 and the wafers 200. The secondnozzle 249 b is disposed in the flank of the wafer arrangement regionwhere the wafers 200 are arranged and horizontally surrounds the waferarrangement region. The second nozzle 249 b is configured as an L-likelong nozzle and has its horizontal portion disposed to penetrate throughthe lower side wall of the reaction tube 203 and its vertical portiondisposed to rise from at least one end of the wafer arrangement regiontoward the other end thereof. A plurality of gas supply holes 250 bthrough which gas is supplied is disposed at a side surface of thesecond nozzle 249 b. The gas supply holes 250 b are opened toward thecenter of the reaction tube 203 to supply gas toward the wafers 200. Thegas supply holes 250 b are disposed to span from the bottom to top ofthe reaction tube 203 at a predetermined opening pitch. Each of the gassupply holes 250 b have the same opening area. A second gas supplysystem is mainly constituted by the second gas supply pipe 232 b, themass flow controller 241 b, the valve 243 b and the second nozzle 249 b.In addition, a second inert gas supply system is mainly constituted bythe second inert gas supply pipe 232 e, the mass flow controller 241 eand the valve 243 e.

A mass flow controller (MFC) 241 c as a flow rate controller (a flowrate control unit) and an opening/closing valve 243 c are disposed inthe third gas supply pipe 232 c in this order from the upstreamdirection. In addition, a third inert gas supply pipe 232 f is connectedto the downstream side of the valve 243 c of the third gas supply pipe232 c. A mass flow controller (MFC) 241 f as a flow rate controller (aflow rate control unit) and an opening/closing valve 243 f are disposedin the third inert gas supply pipe 232 f in this order from the upstreamdirection. In addition, the above-mentioned third nozzle 249 c isconnected to a leading end of the third gas supply pipe 232 c. The thirdnozzle 249 c is vertically disposed along the inner wall of the reactiontube 203 in a circular arc-shaped space between the inner wall of thereaction tube 203 and the wafers 200. The third nozzle 249 c is disposedin the flank of the wafer arrangement region where the wafers 200 arearranged and horizontally surrounds the wafer arrangement region. Thethird nozzle 249 c is configured as an L-like long nozzle and has itshorizontal portion disposed to penetrate through the lower side wall ofthe reaction tube 203 and its vertical portion disposed to rise from atleast one end of the wafer arrangement region toward the other endthereof. A plurality of gas supply holes 250 c through which gas issupplied is disposed in a side surface of the third nozzle 249 c. Thegas supply holes 250 c are opened toward the center of the reaction tube203 to supply gas toward the wafers 200. The gas supply holes 250 c aredisposed to span from the bottom to top of the reaction tube 203 at apredetermined opening pitch. Each of the gas supply holes 250 c have thesame opening area. A third gas supply system is mainly constituted bythe third gas supply pipe 232 c, the mass flow controller 241 c, thevalve 243 c and the third nozzle 249 c. In addition, a third inert gassupply system is mainly constituted by the third inert gas supply pipe232 f, the mass flow controller 241 f and the valve 243 f.

In the gas supply systems, gas is transferred via the nozzles 249 a, 249b and 249 c arranged in the circular arc-shaped longitudinal spacedefined by the inner wall of the reaction tube 203 and ends of theplurality of loaded wafers 200 and supplied into the reaction tube 203near the wafers 200 from the gas supply holes 250 a, 250 b and 250 copened in the nozzles 249 a, 249 b and 249 c. The gas supplied into thereaction tube 203 mainly flows in a horizontal direction, that is, adirection in parallel to the surface of the wafers 200 in the reactiontube 203. This configuration provides an advantage of uniformlysupplying the gas to the wafers 200 and forming a uniform thickness of afilm on the wafers 200. Although a residual gas after the reaction flowstoward the exhaustion mechanism, that is, the exhaustion pipe 231, adirection of flow of the residual gas is specified by a position of theexhaustion mechanism without being limited to the vertical direction.

Raw material gas (first raw material gas) containing, for example, afirst metal element and a halogen element as a first raw material issupplied from the first gas supply pipe 232 a into the process chamber201 via the mass flow controller 241 a, the valve 243 a and the firstnozzle 249 a. Examples of the first metal element may include transitionmetal elements such as titanium (Ti), tantalum (Ta), hafnium (Hf),zirconium (Zr), molybdenum (Mo), tungsten (W) and the like, and examplesof the halogen element may include chlorine (Cl), fluorine (F) and thelike. The first raw material gas may, for example, include a rawmaterial gas containing titanium (Ti) and chlorine (Cl), such astitanium chloride (i.e., titanium tetrachloride (TiCl₄)). If liquid rawmaterial, such as TiCl₄, which is in a liquid state at room temperatureand atmospheric pressure, is used, the liquid raw material may besupplied as raw material gas after being vaporized by a vaporizingsystem (not shown) such as a vaporizer or a bubbler.

Raw material gas (second raw material gas) containing, for example, asecond metal element and a carbon element as a second raw material issupplied from the second gas supply pipe 232 b into the process chamber201 via the mass flow controller 241 b, the valve 243 b and the secondnozzle 249 b. Examples of the second metal element may includetransition metal elements such as titanium (Ti), tantalum (Ta), hafnium(Hf), zirconium (Zr), molybdenum (Mo), tungsten (W) and the like. Thesecond raw material gas may include a substituent, such as a methylgroup, a cyclopentadienyl group, an ethyl group or the like, whichcontains carbon (C) and hydrogen (H). That is, the second raw materialgas may be a raw material which contains a transition metal element,carbon and hydrogen. As an example, the second raw material gas mayinclude a raw material gas, such as Hf[C₅H₄(CH₃)]₂(CH₃)₂ gas or thelike, which contains hafnium (Hf), carbon (C) and hydrogen (H).Hf[C₅H₄(CH₃)]₂(CH₃)₂ is a raw material which contains a methyl group anda cyclopentadienyl group. If solid raw material, such asHf[C₅H₄(CH₃)]₂(CH₃)₂, which is in a solid state at room temperature andatmospheric pressure, is used, the solid raw material may be supplied asraw material gas after being heated or dissolved in a solvent, such asethylcyclohexane (ECH), tetrahydrofuran (THF) or the like, into a liquidstate which is then vaporized by a vaporizing system (not shown) such asa vaporizer or a bubbler.

Gas (nitrogen-containing gas) which contains, for example, nitrogen (N)as a nitridation raw material is supplied from the third gas supply pipe232 c into the process chamber 201 via the mass flow controller 241 c,the valve 243 c and the third nozzle 249 c. An example of thenitrogen-containing gas may include ammonia (NH₃) gas.

For example, nitrogen (N₂) gas is supplied from the inert gas supplypipes 232 d, 232 e and 232 f into the process chamber 201 via the massflow controllers 241 d, 241 e and 241 f, the valves 243 d, 243 e and 243f and the nozzles 249 a, 249 b and 249 c, respectively.

When the gases are flown from the gas supply pipes as described above, afirst raw material gas supply system is constituted by the first gassupply system, a second raw material gas supply system is constituted bythe second gas supply system, and a nitridation gas supply system(nitrogen-containing gas system) is constituted by the third gas supplysystem. When the nitridation gas is a reaction gas, a reaction gassupply system is constituted by the nitridation gas supply system. Whenthe first raw material gas and the second raw material gas are rawmaterial gases, a raw material gas supply system is constituted by thefirst raw material gas supply system and the second raw material gassupply system. In some embodiments, the first raw material gas supplysystem, the second raw material gas supply system and the nitridationgas supply system may be referred to as a first raw material supplysystem, a second raw material supply system and a nitridation rawmaterial supply system, respectively.

The exhaustion pipe 231 to exhaust the internal atmosphere of theprocess chamber 201 is disposed in the reaction tube 203. As shown inFIG. 2, when viewed from a cross section, the exhaustion pipe 231 isdisposed in a position opposite to a position where the gas supply holes250 a of the first nozzle 249 a, the gas supply holes 250 b of thesecond nozzle 249 b and the gas supply holes 250 c of the third nozzle249 c of the reaction tube 203 are disposed, that is, a positionopposite to the gas supply holes 250 a, 250 b and 250 c with the wafers200 interposed therebetween. In addition, as shown in FIG. 1, whenviewed from a longitudinal section, the exhaustion pipe 231 is disposedbelow a position where the gas supply holes 250 a, 250 b and 250 c aredisposed. With this configuration, gas supplied from the gas supplyholes 250 a, 250 b and 250 c to the neighborhood of the wafers 200 inthe process chamber 201 flows in a horizontal direction, that is, adirection in parallel to surfaces of the wafers 200, flows downward, andthen is exhausted out of the exhaustion pipe 231. The main flow of gasin the process chamber 201 becomes a flow in the horizontal direction,as described previously.

The exhaustion pipe 231 is connected with a vacuum pump 246 as a vacuumexhaustion device via a pressure sensor 245 as a pressure detector(pressure detecting part) for detecting the internal pressure of theprocess chamber 201 and an APC (Auto Pressure Controller) valve 244 as apressure regulator (pressure regulating part). The APC valve 244 is avalve configured to perform vacuum exhaustion and vacuum exhaustion stopin the process chamber 201 by opening/closing the valve with the vacuumpump 246 actuated and adjust the internal pressure of the processchamber 201 by regulating a valve position with the vacuum pump 246actuated. An exhaustion system is mainly constituted by the exhaustionpipe 231, the APC valve 244 and the pressure sensor 245. The vacuum pump246 may be also considered to be included in the exhaustion system. Theexhaustion system is configured to perform vacuum exhaustion such thatthe internal pressure of the process chamber 201 is set to apredetermined pressure (a degree of vacuum) by regulating the valveposition of the APC valve 244 based on pressure information detected bythe pressure sensor 245 while actuating the vacuum pump 246.

A seal cap 219, which functions as a furnace opening cover forair-tightly blocking the bottom opening of the reaction tube 203, isdisposed below the reaction tube 203. The seal cap 219 is configured tocontact the bottom of the reaction tube 203 from below in the verticaldirection. The seal cap 219 is made of, for example, metal such asstainless steel or the like and has a disc shape. An O-ring 220 as aseal member contacting the bottom of the reaction tube 203 is disposedin the top side of the seal cap 219. A rotation mechanism 267 to rotatethe boat 217 as a substrate support, which will be described later, isdisposed below the seal cap 219. A shaft 255 of the rotation mechanism267 is connected to the boat 217 through the seal cap 219. The rotationmechanism 267 is configured to rotate the wafers 200 by rotating theboat 217. The seal cap 219 is configured to be vertically elevated by aboat elevator 115 as an elevation mechanism vertically disposed outsidethe reaction tube 203. The boat elevator 115 is configured to carry theboat 217 in and out of the process chamber 201 by elevating the seal cap219. That is, the boat elevator 115 is configured as a transfer device(transfer mechanism) to transfer the boat 217, i.e., the wafers 200, inand out of the process chamber 201.

The boat 217, which is utilized as the substrate support, is made of,for example, a heat resistant material such as quartz, silicon carbideor the like and is configured to support the wafers 200 horizontallystacked in multiple stages with the center of the wafers 200concentrically aligned. In addition, a heat insulating member 218 madeof, for example, a heat resistant material such as quartz, siliconcarbide or the like is disposed below the boat 217 and is configured tomake it difficult for heat from the heater 207 to be transferred to theseal cap 219. The heat insulating member 218 may be constituted by aplurality of heat insulating plates, each made of a heat resistantmaterial such as quartz, silicon carbide or the like, and a heatinsulating plate holder to support these heat insulating plateshorizontally in multiple stages.

A temperature sensor 263 as a temperature detector is disposed withinthe reaction tube 203. Based on temperature information detected by thetemperature sensor 263, a state of electric conduction to the heater 207is adjusted such that the interior of the process chamber 201 has anintended temperature distribution. The temperature sensor 263 has aL-like shape, like the nozzles 249 a, 249 b and 249 c and is disposedalong the inner wall of the reaction tube 203.

As shown in FIG. 3, a controller 121 as a control unit (control means)is constituted by a computer including a CPU (Central Processing Unit)121 a, a RAM (Random Access Memory) 121 b, a storage device 121 c and anI/O port 121 d. The RAM 121 b, the storage device 121 c and the I/O port121 d are configured to exchange data with the CPU 121 a via an internalbus 121 e. An input/output device 122 constituted by, for example, atouch panel or the like is connected to the controller 121.

The storage device 121 c is constituted by, for example, a flash memory,a HDD (Hard Disk Drive) or the like. Control programs to control anoperation of the substrate processing apparatus and process recipesdescribing substrate processing procedures and conditions, which will bedescribed later, are readably loaded (stored) in the storage device 121c. The process recipes function as programs to cause the controller 121to execute procedures in substrate processing which will be describedlater. Hereinafter, these process recipes and control programs arecollectively simply referred to as programs. As used herein, the term“programs” may be intended to include process recipes only, controlprograms only, or both thereof. The RAM 121 b is configured as a memoryarea (work area) in which programs and data read by the CPU 121 a aretemporarily stored.

The I/O port 121 d is connected to the above-mentioned mass flowcontrollers 241 a, 241 b, 241 c, 241 d, 241 e and 241 f, valves 243 a,243 b, 243 c, 243 d, 243 e and 243 f, pressure sensor 245, APC valve244, vacuum pump 246, heater 207, temperature sensor 263, rotationmechanism 267, boat elevator 115 and so on.

The CPU 121 a is configured to read and execute a control program fromthe storage device 121 c and read a process recipe from the storagedevice 121 c according to an operation command input from theinput/output device 122. The CPU 121 a is further configured to controla flow rate adjustment operation of various gases by the mass flowcontrollers 241 a, 241 b, 241 c, 241 d, 241 e and 241 f, anopening/closing operation of the valves 243 a, 243 b, 243 c, 243 d, 243e and 243 f, an opening/closing operation of the APC valve 244, apressure adjustment operation by the APC valve 244 based on the pressuresensor 245, a temperature adjustment operation of the heater 207 basedon the temperature sensor 263, start and stop of the vacuum pump 246,rotation and a rotation speed adjustment operation of the boat 217 bythe rotation mechanism 267, an elevation operation by the boat elevator115, etc., according to contents of the read process recipe.

The controller 121 may be configured as a general-purpose computerwithout being limited to a dedicated computer. For example, in theembodiment, the controller 121 may be configured by preparing anexternal storage device (for example, a magnetic tape, a magnetic disksuch as a flexible disk or a hard disk, an optical disk such as CD orDVD, a magneto-optical disk such as MO, and a semiconductor memory suchas a USB memory or a memory card) 123 which stores the above-describedprograms and installing the programs from the external storage device123 into the general-purpose computer. A means for providing theprograms for the computer is not limited to the case where the programsare provided through the external storage device 123. For example, theprograms may be provided using a communication means such as Internet, adedicated line or the like, without the external storage device 123. Thestorage device 121 c and the external storage device 123 are implementedwith a computer readable recording medium and will be hereinaftercollectively simply referred to as a recording medium. The term“recording medium” may include the storage device 121 c only, theexternal storage device 123 only, or both thereof.

(2) Substrate Processing

As one of processes of manufacturing a semiconductor device using thevertical treatment furnace 202 of the above-described substrateprocessing apparatus, an example of sequence of forming a metalcarbonitride film on a substrate will be now described. In the followingdescription, operations of various components constituting the substrateprocessing apparatus are controlled by the controller 121.

<First Sequence>

A first sequence of a substrate processing according to some embodimentswill be first described. FIG. 4 is a view illustrating a flow of filmformation in a first sequence of a substrate processing, according tosome embodiments. FIG. 6 is a view illustrating timings of gas supply inthe first sequence.

In the first sequence, a titanium carbonitride film (TiCN film) having apredetermined thickness is formed on a wafer 200 by alternatelyperforming (i) a first process of alternately supplying a first rawmaterial, which contains titanium (Ti) and chlorine (Cl), and a secondraw material, which contains hafnium (Hf) and carbon, to the wafer 200in the process chamber 201 by a first predetermined number of times toform a titanium carbide layer (TiC layer), which contains titanium (Ti)and carbon (C), on the wafer 200, and (ii) a second process of supplyinga nitridation raw material to the wafer 200 in the process chamber 201to form a titanium carbonitride layer (TiCN layer), which containstitanium, carbon and nitrogen, by nitrating the TiC layer, by a secondpredetermined number of times.

As used herein, the phrase “alternately supplying a first raw materialand a second raw material by a first predetermined number of times” mayrefer to performing a set of supply of a first raw material and a secondraw material once or more than once. That is, this phrase may refer toperforming this set one or more number of times. For example, in someembodiments this set may be performed more than once in order to obtaina TiCN film having a relatively high concentration of C. Increase in thenumber of times for performance of this set may lead to increase in theconcentration of C in the TiCN film. In other embodiments, this set maybe performed by the decreased number of times (for example, once) inorder to obtain a TiCN film having a relatively low concentration of C.

As used herein, the phrase “alternately performing a first process ofalternately supplying a first raw material and a second raw material bya first predetermined number of times and a second process of supplyinga nitridation raw material, by a second predetermined number of times”may refer to including performing one cycle of a first process ofalternately supplying a first raw material and a second raw material bythe first predetermined number of times and a second process ofsupplying a nitridation raw material, either once or more than once.That is, this phrase means performing this cycle one or more number oftimes.

FIGS. 4 and 6 are examples of supplying the first raw material to thewafer 200 in the process chamber 201 to form the TiC layer and thensupplying the second raw material. In other words, FIGS. 4 and 6illustrate examples of supplying the first raw material earlier than thesecond raw material. However, the order of supplying the first rawmaterial and the second raw material is not limited to these examples.For example, the second raw material may be supplied earlier than thefirst raw material.

The first sequence of the substrate processing will be described belowin further detail. In this example, TiCl₄ gas, Hf[C₅H₄(CH₃)]₂(CH₃)₂ gasand NH₃ gas may be used for the first raw material, the second rawmaterial and the nitridation raw material, respectively, and thetitanium carbonitride film (TiCN film) may be formed as a metalcarbonitride film on the wafer 200 according to the film formation flowof FIG. 4 and the film formation sequence of FIG. 6.

As used herein, the term “metal film” means a film made of a conductivematerial which contains a metal element, including, but not limted to, aconductive metal film made of metal only, a conductive metal nitridefilm, a conductive metal oxide film, a conductive metal oxynitride film,a conductive metal composite film, a conductive metal ally film, aconductive metal silicide film, a conductive metal carbide film, aconductive metal carbonitride film, etc. The titanium carbonitride filmis one type of the conductive metal carbonitride film and the titaniumcarbide film is one type of the conductive metal carbide film.

<Wafer Charge and Boat Load>

When a plurality of wafers 200 is loaded on the boat 217 (wafer charge),the boat 217 supporting the plurality of wafers 200 is lifted and loadedinto the process chamber 201 by the boat elevator 115 (boat load). Inthis state, the seal cap 219 seals the bottom of the reaction tube 203via the O-ring 220.

<Pressure Adjustment and Temperature Adjustment>

The interior of the process chamber 201 is vacuum-exhausted by thevacuum pump 246 to set the interior to a desired pressure (degree ofvacuum). At this time, the internal pressure of the process chamber 201is measured by the pressure sensor 245 and the APC valve 244 isfeedback-controlled based on the measured pressure information (pressureadjustment). The vacuum pump 246 remains activated at least until thewafers 200 are completely processed. The interior of the process chamber201 is heated by the heater 207 to set the interior to a desiredtemperature. At this time, a state of electric conduction to the heater207 is feedback-controlled based on the temperature information detectedby the temperature sensor 263 such that the interior of the processchamber 201 has a desired temperature distribution (temperatureadjustment). The heating of the interior of the process chamber 201 bythe heater 207 continues at least until the wafers 200 are completelyprocessed. Subsequently, the boat 217 and the wafers 200 begin to berotated by the rotation mechanism 267. The rotation of the boat 217 andthe wafers 200 by the rotation mechanism 267 continues at least untilthe wafers 200 are completely processed. Thereafter, the following threesteps are sequentially performed.

<Step 1> <TiCl₄ Gas Supply>

The valve 243 a of the first gas supply pipe 232 a is opened to flowTiCl₄ gas into the first gas supply pipe 232 a. A flow rate of the TiCl₄gas flowing into the first gas supply pipe 232 a is regulated by themass flow controller 241 a. The TiCl₄ gas with its flow rate regulatedis supplied from the gas supply hole 250 a of the first nozzle 249 ainto the process chamber 201 and is exhausted from the exhaustion pipe231. At this time, the TiCl₄ gas is supplied to the wafers 200. At thesame time, the valve 243 d is opened to flow inert gas such as N₂ gas orthe like into the first inert gas supply pipe 232 d. A flow rate of theN₂ gas flowing into the first inert gas supply pipe 232 d is regulatedby the mass flow controller 241 d. The N₂ gas with its flow rateregulated is supplied into the process chamber 201, along with the TiCl₄gas, and is exhausted from the exhaustion pipe 231. At this time, inorder to prevent the TiCl₄ gas from being introduced into the secondnozzle 249 b and the third nozzle 249 c, the valves 243 e and 243 f areopened to flow the N₂ gas into the second inert gas supply pipe 232 eand the third inert gas supply pipe 232 f. The N₂ gas is supplied intothe process chamber 201 via the second gas supply pipe 232 b, the thirdgas supply pipe 232 c, the second nozzle 249 b and the third nozzle 249c and is exhausted from the exhaustion pipe 231.

At this time, the APC valve 244 is appropriately regulated to set theinternal pressure of the process chamber 201 to fall within a range of,for example, 10 to 2000 Pa. The flow rate of TiCl₄ gas controlled by themass flow controller 241 a is set to fall within a range of, forexample, 10 to 2000 sccm. The flow rates of N₂ gases controlled by themass flow controllers 241 d, 241 e and 241 f are set to fall within arange of, for example, 100 to 10000 sccm. Time period during which theTiCl₄ gas is supplied to the wafers 200, that is, gas supply time(irradiation time), is set to fall within a range of, for example, 0.1to 120 seconds. At this time, the heater 207 is set to a temperaturesuch that the temperature of the wafers 200 is set to fall within arange of, for example, 200 to 450 degrees C. If the temperature of thewafers 200 is less than 200 degrees C., a TiC layer formed byalternately performing Step 1 and Step 2, which will be described later,by the predetermined number of times, does not react with NH₃ suppliedin Step 3, which will be described later, thereby preventing a TiCNlayer from being formed in Step 3. If the temperature of the wafers 200exceeds 450 degrees C., a gas phase reaction becomes dominant, which mayresult in deteriorated uniformity of film thickness and difficulty incontrol thereof. Thus, in some embodiments, the temperature of thewafers 200 will mainly fall within a range of 200 to 450 degrees C.

The supply of TiCl₄ gas results in formation of a titanium-containinglayer having a thickness of, for example, less than one atomic layer toseveral atomic layers on underlayers on surfaces of the wafers 200. Thetitanium-containing layer may be a TiCl₄ chemical adsorption layer or atitanium layer (Ti layer) or both thereof. In this example, thetitanium-containing layer may be a layer which contains titanium (Ti)and chlorine (Cl).

In this example, the titanium layer includes a continuous layer made oftitanium (Ti), a discontinuous layer, or a titanium thin film composedof a combination of these continuous and discontinuous layers. Thecontinuous layer made of Ti is sometimes referred to as a titanium thinfilm. Ti of which the titanium layer is made includes one which is notcompletely decoupled from Cl.

The TiCl₄ chemical adsorption layer includes a TiCl₄ molecule continuouschemical adsorption layer and a TiCl₄ molecule discontinuous chemicaladsorption layer. That is, the TiCl₄ chemical adsorption layer includesa chemical adsorption layer having a thickness of one molecular layer orless constituted by TiCl₄ molecules. The TiCl₄ molecules constitutingthe TiCl₄ chemical adsorption layer include those (TiCl_(x) molecules)in which Ti is partially decoupled from Cl. That is, the TiCl₄ chemicaladsorption layer includes TiCl₄ molecule and/or TiCl_(x) continuous anddiscontinuous chemical adsorption layers. As used herein, the phrase“layer having a thickness of less than one atomic layer” means an atomiclayer discontinuously formed and the phrase “layer having a thickness ofone atomic layer” means an atomic layer continuously formed. Similarly,the phrase “layer having a thickness of less than one molecular layer”means a molecular layer discontinuously formed and the phrase “layerhaving a thickness of one molecular layer” means a molecular layercontinuously formed.

Under the condition where the TiCl₄ gas is self-decomposed (pyrolyzed),that is, under the condition where a pyrolytic reaction of the TiCl₄ gasis produced, Ti is deposited on the wafers 200, thereby forming thetitanium layer. Under the condition where the TiCl₄ gas is notself-decomposed (pyrolyzed), that is, under the condition where nopyrolytic reaction of the TiCl₄ gas is produced, the TiCl₄ gas ischemically absorbed and deposited on the wafers 200, thereby forming theTiCl₄ gas chemical adsorption layer. Forming the TiCl₄ gas chemicaladsorption layer on the wafers 200 can provide a higher film formationrate than forming the titanium layer on the wafers 200.

If the thickness of the titanium-containing layer formed on the wafers200 exceeds several atomic layers, nitridation reaction in Step 3, whichwill be described later, may not occur in the entire titanium-containinglayer. The minimum of thickness of the titanium-containing layer whichcan be formed on the wafers 200 is less than one atomic layer.Accordingly, the thickness of the titanium-containing layer may be setto fall within a range of less than one atomic layer to several atomiclayers. When the thickness of the titanium-containing layer is not lessthan one atomic layer, i.e., one atomic layer or less, nitridationreaction in Step 3, which will be described later, can be relativelyexpedited and time required for the nitridation reaction in Step 3 canbe shortened. Time required for the formation of the titanium-containinglayer in Step 1 can be also shortened. As a result, processing time percycle and hence total processing time can be shortened. In other words,a film formation rate can be increased. In addition, when the thicknessof the titanium-containing layer is not less than one atomic layer,controllability for uniform film thickness can be improved.

<Residual Gas Removal>

After the titanium-containing layer is formed, the valve 243 a of thefirst gas supply pipe 232 a is closed to stop the supply of the TiCl₄gas. At this time, with the APC valve 244 of the exhaustion pipe 231opened, the interior of the process chamber 201 is vacuum-exhausted bythe vacuum pump 246 and unreacted TiCl₄ gas remaining in the processchamber 201 or TiCl₄ gas which remains after contributing to theformation of the titanium-containing layer is excluded from the processchamber 201. At this time, with the valves 243 d, 243 e and 243 fopened, the supply of the N₂ gas into the process chamber 201 ismaintained. The N₂ gas acts as purge gas which is capable of furtherimproving the effect of excluding the unreacted TiCl₄ gas remaining inthe process chamber 201 or the TiCl₄ gas which remains aftercontributing to the formation of the titanium-containing layer from theprocess chamber 201.

The residual gas in the process chamber 201 may not be completelyexcluded and the interior of the process chamber 201 may not becompletely purged. If an amount of the residual gas in the processchamber 201 is very small, this has no adverse effect on the subsequentStep 2. In this case, there is no need to provide a high flow rate of N₂gas supplied into the process chamber 201. For example, the same volumeof N₂ gas as the reaction tube 203 (the process chamber 201) may besupplied into the process chamber 201 to purge the interior of theprocess chamber 201 to such a degree that this has no adverse effect onStep 2. In this way, when the interior of the process chamber 201 is notcompletely purged, purge time can be shortened, thereby improving athroughput. This can also limit consumption of N₂ gas to the minimumrequired for purging.

Examples of the first raw material gas may include raw material gas,which contains titanium (Ti) and fluorine (F), such as titaniumfluoride, i.e., tetrafluoride (TiF₄), and the like, in addition to TiCl₄gas. Examples of the inert gas may include rare gases such as Ar gas, Hegas, Ne gas, Xe gas and the like, in addition to N₂ gas.

<Step 2>

<Hf[C₅H₄(CH₃)]₂(CH₃)₂ Gas Supply>

After Step 1 is completed to remove the residual gas from the processchamber 201, the valve 243 b of the second gas supply pipe 232 b isopened to flow Hf[C₅H₄(CH₃)]₂(CH₃)₂ gas into the second gas supply pipe232 b. A flow rate of the Hf[C₅H₄(CH₃)]₂(CH₃)₂ gas flowing into thesecond gas supply pipe 232 b is regulated by the mass flow controller241 b. The Hf[C₅H₄(CH₃)]₂(CH₃)₂ gas with its flow rate regulated issupplied from the gas supply hole 250 b of the second nozzle 249 b intothe process chamber 201 and is exhausted from the exhaustion pipe 231.At this time, the Hf[C₅H₄(CH₃)]₂(CH₃)₂ gas is supplied to the wafers200. At the same time, the valve 243 e is opened to flow N₂ gas or thelike into the second inert gas supply pipe 232 e. A flow rate of the N₂gas flowing into the second inert gas supply pipe 232 e is regulated bythe mass flow controller 241 e. The N₂ gas with its flow rate regulatedis supplied into the process chamber 201, along with theHf[C₅H₄(CH₃)]₂(CH₃)₂ gas, and is exhausted from the exhaustion pipe 231.At this time, in order to prevent the Hf[C₅H₄(CH₃)]₂(CH₃)₂ gas frombeing introduced into the first nozzle 249 a and the third nozzle 249 c,the valves 243 d and 243 f are opened to flow the N₂ gas into the firstinert gas supply pipe 232 d and the third inert gas supply pipe 232 f.The N₂ gas is supplied into the process chamber 201 via the first gassupply pipe 232 a, the third gas supply pipe 232 c, the first nozzle 249a and the third nozzle 249 c and is exhausted from the exhaustion pipe231.

At this time, the APC valve 244 is appropriately regulated to set theinternal pressure of the process chamber 201 to fall within a range of,for example, 10 to 2000 Pa, as in Step 1. The flow rate ofHf[C₅H₄(CH₃)]₂(CH₃)₂ gas controlled by the mass flow controller 241 b isset to fall within a range of, for example, 10 to 2000 sccm. The flowrates of N₂ gases controlled by the mass flow controllers 241 e, 241 dand 241 f are set to fall within a range of, for example, 100 to 10000sccm. The time period during which the Hf[C₅H₄(CH₃)]₂(CH₃)₂ gas issupplied to the wafers 200, that is, gas supply time (irradiation time),is set to fall within a range of, for example, 0.1 to 120 seconds. Atthis time, the heater 207 is set to a temperature such that thetemperature of the wafers 200 is set to fall within a range of, forexample, 200 to 450 degrees C., as in Step 1.

The supply of Hf[C₅H₄(CH₃)]₂(CH₃)₂ gas results in reaction of thetitanium-containing layer (the TiCl₄ and/or TiCl_(x) chemical adsorptionlayer or the Ti layer) formed on the wafers 200 in Step 1 with theHf[C₅H₄(CH₃)]₂(CH₃)₂ gas. At this time, a gaseous material is mainlyproduced by reaction of chlorine (Cl) in the titanium-containing layerformed on the wafers 200 in Step 1 with the Hf[C₅H₄(CH₃)]₂ in theHf[C₅H₄(CH₃)]₂(CH₃)₂ gas and is discharged as gas. At this time,chlorine (Cl) in the titanium-containing layer may react with a methylgroup (CH₃) or a cyclopentadienyl group (C₅H₄) in theHf[C₅H₄(CH₃)]₂(CH₃)₂ gas. In this case, as the Hf[C₅H₄(CH₃)]₂(CH₃)₂ isdecomposed, hafnium (Hf) and hydrogen (H) in Hf[C₅H₄(CH₃)]₂(CH₃)₂ mayreact with Cl in the titanium-containing layer to produce a gaseousmaterial to be discharged as gas. In this way, in Step 2, Cl in TiCl₄and Hf in Hf[C₅H₄(CH₃)]₂(CH₃)₂ are transformed into a gaseous materialto be discharged. That is, Cl in TiCl₄ and Hf in Hf[C₅H₄(CH₃)]₂(CH₃)₂are transformed into a gaseous material, which contains Cl, and agaseous material, which contains Hf, and/or a gaseous material, whichcontains Cl and Hf, all of which are to be discharged. The remaining Cland Hf which are not discharged as gas are transformed into a gaseousmaterial to be discharged as gas when TiCl₄ gas is supplied in Step 1 tobe performed next. During these processes, some of carbons (C) decoupledfrom hydrogen (H) and some of methyl groups (CH₃) separated fromhydrogen by the decomposition of the Hf[C₅H₄(CH₃)]₂(CH₃)₂ gas remainwithout being discharged as gas and are bonded to Ti in thetitanium-containing layer. This allows the titanium-containing layer tobe modified as a titanium carbide layer (TiC layer) which contains Tiand C. The TiC layer becomes a layer which contains Ti and C having athickness of less than one atomic layer to several atomic layers.

<Residual Gas Removal>

Thereafter, the valve 243 b of the second gas supply pipe 232 b isclosed to stop the supply of the Hf[C₅H₄(CH₃)]₂(CH₃)₂ gas. At this time,with the APC valve 244 of the exhaustion pipe 231 opened, the interiorof the process chamber 201 is vacuum-exhausted by the vacuum pump 246and unreacted Hf[C₅H₄(CH₃)]₂(CH₃)₂ gas remaining in the process chamber201 or Hf[C₅H₄(CH₃)]₂(CH₃)₂ gas which remains after contributing to theformation of the TiC layer, and reactive by-products are excluded fromthe process chamber 201. At this time, with the valves 243 e, 243 d and243 f opened, the supply of the N₂ gas into the process chamber 201 ismaintained. The N₂ gas acts as purge gas which is capable of furtherimproving the effect of excluding the unreacted Hf[C₅H₄(CH₃)]₂(CH₃)₂ gasremaining in the process chamber 201 or the Hf[C₅H₄(CH₃)]₂(CH₃)₂ gaswhich remains after contributing to the formation of thetitanium-containing layer, and the reactive by-products from the processchamber 201.

The residual gas in the process chamber 201 may not be completelyexcluded and the interior of the process chamber 201 may not becompletely purged. If an amount of the residual gas in the processchamber 201 is very small, this has no adverse effect on the subsequentStep 3. In this case, there is no need to provide a high flow rate of N₂gas supplied into the process chamber 201. For example, the same volumeof N₂ gas as the reaction tube 203 (the process chamber 201) may besupplied into the process chamber 201 to purge the interior of theprocess chamber 201 to such a degree that this has no adverse effect onStep 3. In this way, when the interior of the process chamber 201 is notcompletely purged, purge time can be shortened, thereby improving athroughput. This can also limit consumption of N₂ gas to the minimumrequired for purging.

Examples of the second raw material gas may include Zr[C₅H₄(CH₃)]₂(CH₃)₂gas and the like in addition to Hf[C₅H₄(CH₃)]₂(CH₃)₂ gas. Examples ofthe second raw material gas may also include raw material gas whichcontains an ethyl group (C₂H₅) reacting with chlorine, in addition tothe raw material gas which contains the methyl group (CH₃) and thecyclopentadienyl group (C₅H₄) reacting with chlorine, such asHf[C₅H₄(CH₃)]₂(CH₃)₂ gas. For example, the second raw material may betetrakis(methylethylamino)hafnium (Hf[N(C₂H₅)(CH₃)]₄, abbreviated asTEMAHf) gas, tetrakis(methylethylamino)zirconium (Zr[N(C₂H₅)(CH₃)]₄,abbreviated as TEMAZr) gas, tetrakis(dimethylamino)hafnium(Hf[N(CH₃)₂]₄, abbreviated as TDMAHf) gas,tetrakis(dimethylamino)titanium (Ti[N(CH₃)₂]₄, abbreviated as TDMATi)gas, trimethylaluminum (Al(CH₃)₃, abbreviated as TMA) and the like. Inorder to provide the above-described reaction with high efficiency, araw material gas may be used that contains the methyl group (CH₃) andthe cyclopentadienyl group (C₅H₄), such as the Hf[C₅H₄(CH₃)]₂(CH₃)₂ gasor the Zr[C₅H₄(CH₃)]₂(CH₃)₂ gas. The TEMAHf gas and the TEMAZr gas areraw material gas containing a methyl group and an amino group. TMA gasis raw material gas containing a methyl group. It may be said that theHf[C₅H₄(CH₃)]₂(CH₃)₂ gas, the Zr[C₅H₄(CH₃)]₂(CH₃)₂ gas and the TMA gasare nitrogen-free raw material gas in that they contain no nitrogen. Thesecond raw material gas may be an unstable raw material gas. Examples ofthe inert gas may include rare gases such as Ar gas, He gas, Ne gas, Xegas and the like, in addition to N₂ gas.

Thereafter, a TiC layer having a predetermined thickness is formed byperforming one set of the above-described Steps 1 and 2 by thepredetermined number of times. FIG. 6 shows that this set is performed mtimes. The number of times m of performance of the set is, for example,1 to 200, 1 to 100, or 1 to 20. More specifically, the number of times mof performance of the set may be several or 2 to 6. Controlling(adjusting) the number of times m of performance of the set makes itpossible to control a concentration of C in a TiCN film to be finallyformed. In order to obtain a TiCN film having a relatively high Cconcentration, the set may be performed several times rather than once.For example, in order to form a TiCN film as a gate electrode having a Cconcentration of 5 to 20 at %, set may be performed several times.Increase in the number of times of performance of the set can lead toincrease in the C concentration of the TiCN film. In order to obtain aTiCN film having a relatively low C concentration, the number of times mof performance of the set may be small (for example, one).

<Step 3> <NH₃ Gas Supply>

After the TiC layer having the predetermined thickness is formed and theresidual gas in the process chamber 201 is removed, the valve 243 c ofthe third gas supply pipe 232 c is opened to flow NH₃ gas into the thirdgas supply pipe 232 c. A flow rate of the NH₃ gas flowing into the thirdgas supply pipe 232 c is regulated by the mass flow controller 241 c.The NH₃ gas with its flow rate regulated is supplied from the gas supplyhole 250 c of the third nozzle 249 c into the process chamber 201. TheNH₃ gas supplied into the process chamber 201 is activated by heat andis exhausted from the exhaustion pipe 231. At this time, the NH₃ gasactivated by the heat is supplied to the wafers 200. At the same time,the valve 243 f is opened to flow N₂ gas into the third inert gas supplypipe 232 f. A flow rate of the N₂ gas flowing into the third inert gassupply pipe 232 f is regulated by the mass flow controller 241 f. The N₂gas is supplied into the process chamber 201, along with the NH₃ gas,and is exhausted from the exhaustion pipe 231. At this time, in order toprevent the NH₃ gas from being introduced into the first nozzle 249 aand the second nozzle 249 b, the valves 243 d and 243 e are opened toflow the N₂ gas into the first inert gas supply pipe 232 d and thesecond inert gas supply pipe 232 e. The N₂ gas is supplied into theprocess chamber 201 via the first gas supply pipe 232 a, the second gassupply pipe 232 b, the first nozzle 249 a and the second nozzle 249 band is exhausted from the exhaustion pipe 231.

When the NH₃ gas is activated by the heat and is flown, the APC valve244 is appropriately regulated to set the internal pressure of theprocess chamber 201 to fall within a range of, for example, 10 to 2000Pa. By setting the internal pressure of the process chamber 201 to sucha relatively high pressure, it becomes possible to thermally activatethe NH₃ gas with non-plasma. In addition, the thermally activated NH₃gas is supplied to produce a soft reaction to soften nitridation whichwill be described later. A flow rate of NH₃ gas controlled by the massflow controller 241 c is set to fall within a range of, for example, 10to 2000 sccm. Flow rates of N₂ gases controlled by the mass flowcontrollers 241 f, 241 d and 241 e are set to fall within a range of,for example, 100 to 10000 sccm. The time period during which thethermally activated NH₃ gas is supplied to the wafers 200, that is, gassupply time (irradiation time), is set to fall within a range of, forexample, 0.1 to 120 seconds. At this time, the heater 207 is set to atemperature such that the temperature of the wafers 200 is set to fallwithin a range of, for example, 200 to 450 degrees C., as in Steps 1 and2.

At this time, gas flowing into the process chamber 201 is the NH₃ gasactivated thermally by increasing the internal pressure of the processchamber 201 into which neither TiCl₄ gas nor Hf[C₅H₄(CH₃)]₂(CH₃)₂ gas isflown. Accordingly, the activated NH₃ gas reacts with at least a portionof the TiC layer which is formed on the wafers 200 in Step 2 andcontains Ti and C, without causing any gas phase reaction. This allowsthe TiC layer to be nitrided and modified into a titanium carbonitridelayer (TiCN layer).

In addition, when the TiC layer is thermally nitrided by the thermallyactivated NH₃ gas and modified (changed) into the TiCN layer, the TiClayer is modified into the TiCN layer while adding nitrogen (N) to theTiC layer. At this time, a Ti—N bond in the TiC layer is increased byaction of the thermal nitridation by the NH₃ gas. That is, the TiC layercan be modified into the TiCN layer while changing a composition ratioin a manner to increase a nitrogen concentration. In addition, bycontrolling process conditions such as the internal pressure of theprocess chamber 201, the gas supply time and so on, it is possible tofinely adjust a percentage of nitrogen (N) in the TiCN layer, i.e., thenitrogen concentration and more minutely control the composition ratioof the TiCN layer.

At this time, the nitridation reaction of the TiC layer is notsaturated. For example, when the TiC layer having a thickness of lessthan one atomic layer to several atomic layers is formed in Steps 1 and2, a portion of the TiC layer may be nitrided. In this case, thenitridation is performed under the condition where the nitridationreaction of the TiC layer is unsaturated to prevent the entire TiC layerhaving the thickness of less than one atomic layer to several atomiclayers from being nitrided. In order to prevent the nitridation reactionof the TiC layer from being saturated, the process conditions in Step 3may be set as the above-mentioned condition.

<Residual Gas Removal>

Thereafter, the valve 243 c of the third gas supply pipe 232 c is closedto stop the supply of the NH₃ gas. At this time, with the APC valve 244of the exhaustion pipe 231 opened, the interior of the process chamber201 is vacuum-exhausted by the vacuum pump 246 and unreacted NH₃ gasremaining in the process chamber 201 or NH₃ gas which remains aftercontributing to the formation of the TiCN layer, and reactiveby-products are excluded from the process chamber 201. At this time,with the valves 243 f, 243 d and 243 e opened, the supply of the N₂ gasinto the process chamber 201 is maintained. The N₂ gas acts as purge gaswhich is capable of further improving the effect of excluding theunreacted NH₃ gas remaining in the process chamber 201 or the NH₃ gaswhich remains after contributing to the formation of thetitanium-containing layer, and the reactive by-products from the processchamber 201.

The residual gas in the process chamber 201 may not be completelyexcluded and the interior of the process chamber 201 may not becompletely purged. If an amount of the residual gas in the processchamber 201 is very small, this has no adverse effect on the subsequentStep 1. In this case, there is no need to provide a high flow rate of N₂gas supplied into the process chamber 201. For example, the same volumeof N₂ gas as the reaction tube 203 (the process chamber 201) may besupplied into the process chamber 201 to purge the interior of theprocess chamber 201 to such a degree that this has no adverse effect onStep 1. In this way, when the interior of the process chamber 201 is notcompletely purged, purge time can be shortened, thereby improving athroughput. This can also limit consumption of N₂ gas to the minimumrequired for purging.

Examples of the nitridation raw material may include diazene (N₂H₂) gas,hydrazine (N₂H₄) gas, N₃H₈ gas and the like, in addition to the NH₃ gas.In addition, these gases may be diluted with rare gases such as Ar gas,He gas, Ne gas, Xe gas and the like.

Thereafter, a titanium carbonitride film (TiCN film) having apredetermined composition and thickness is formed on the wafers 200 byperforming a cycle of a first process of alternately performing Steps 1and 2 by a first predetermined number of times and a second process ofperforming Step 3, by a second predetermined number of times. FIG. 6shows that this cycle may be performed n cycles as the secondpredetermined number of times. Controlling (adjusting) the number oftimes n of performance of the cycle makes it possible to control athickness of a TiCN film to be finally formed. For example, in order toform a TiCN film as a gate electrode having a C concentration of 5 to 20at % and a thickness of 0.1 to 50 nm, the number of times n ofperformance of the cycle falls within a range of 1 to 500. This cyclemay be performed once or several times rather than once. That is, athickness of the TiCN layer formed per cycle may be set to be smallerthan a desired thickness and the cycle may be repeated several timesuntil the TiCN layer reaches the desired thickness. In this way, bysetting the thickness of the TiCN layer formed per cycle to be small andrepeating the cycle several times, it is possible to effect an action ofnitridation performed in Step 3 on the entire TiC layer. In addition, itis possible to nitride the TiCN film more uniformly and moreuniformalize the concentration of N in the TiCN film in the thicknessdirection.

<Purge and Return to Atmospheric Pressure>

Once the film formation process of forming the TiCN film having thepredetermined composition and thickness is completed, inert gas such asN₂ or the like is supplied into the process chamber 201 and is exhaustedfrom the exhaustion pipe 231 such that the interior of the processchamber 201 is purged by the inert gas (gas purge). Thereafter, theinternal atmosphere of the process chamber 201 is substituted with theinert gas (inert gas substitution) and the internal pressure of theprocess chamber 201 returns to the atmospheric pressure (return toatmospheric pressure).

<Boat Unload and Wafer Discharge>

Thereafter, the seal cap 219 is descended by the boat elevator 115 toopen the bottom of the reaction tube 203 while carrying the processedwafers 200 from the bottom of the reaction tube 203 out of the reactiontube 203 with them supported by the boat 217 (boat unload). Thereafter,the processed wafers 200 are discharged out of the boat 217 (waferdischarge).

<Second Sequence>

Next, a second sequence of a substrate processing according to someembodiments will be described.

FIG. 5 is a view illustrating a flow of film formation in the secondsequence of the substrate processing. FIG. 7 is a view illustratingtimings of gas supply in the second sequence.

In the second sequence, a titanium carbide film (TiC film) whichcontains titanium and carbon is formed on a wafer 200 by alternatelysupplying a first raw material, which contains titanium (Ti) andchlorine (Cl), and a second raw material, which contains hafnium (Hf)and carbon (C), to the wafer 200 in the process chamber 201 by thepredetermined number of times. That is, in the second sequence, a TiCfilm having a predetermined composition and thickness is formed on thewafer 200 by performing a cycle of Steps 1 and 2 by the predeterminednumber n of times without performing Step 3 in the first sequence. Thissequence is equal to the first sequence except that the former does notperform Step 3. In addition, this sequence may have the same processconditions as the first sequence.

(3) Certain Advantages

According to the first and second sequences, the TiCN film or the TiCfilm can be formed with high step coverage unlike a deposition methodsuch as a sputtering method. That is, the TiCN film or the TiC film canbe formed with high step coverage on a three-dimensional structurerequiring step coverage.

In addition, according to the first sequence of the embodiment, bycontrolling (adjusting) the number of times m of performance of a set ofSteps 1 and 2, it is possible to adjust a concentration of carbon andnitrogen in the TiC film and form the TiCN film having desiredcharacteristics while controlling a composition ratio. In addition, inorder to obtain a TiCN film having a relatively high C concentration,the set may be performed several times rather than once. For example, inorder to form a TiCN film as a gate electrode having a C concentrationof 5 to 20 at %, this set can be performed several times. Increase inthe number of times of performance of the set can lead to increase inthe C concentration of the TiCN film, thereby relatively decreasing a Nconcentration. In addition, in order to obtain a TiCN film having arelatively low C concentration, the number of times m of performance ofthe set may be small (for example, one). That is, according to the firstsequence of the substrate processing method, it is possible to controlthe C concentration of the TiCN film over a wide range from a highconcentration to a low concentration.

In addition, according to the first sequence, by controlling (adjusting)the number of times n of performance of a cycle of a process ofalternately performing Steps 1 and 2 by the predetermined number oftimes and a process of performing Step 3, it is possible to control athickness of the TiC film. Similarly, also in the second sequence of theembodiment, by controlling (adjusting) the number of times n ofperformance of a cycle of Steps 1 and 2, it is possible to control thethickness of the TiC film.

In addition, according to the first sequence, by setting a thickness ofthe TiCN layer formed per cycle to be smaller than a desired thicknessand repeating the cycle several times until the TiCN layer reaches thedesired thickness, it is possible to effect an action of nitridationperformed in Step 3 on the entire TiC layer. In addition, it is possibleto nitride the TiCN film more uniformly and more uniformalize theconcentration of N in the TiCN film in the thickness direction.

Although various embodiments have been described in the above, thepresent disclosure is not limited to these disclosed embodiments.

For example, it may be suitably applied to form metal carbonitride filmssuch as a tantalum carbonitride film (TaCN film), a hafnium carbonitridefilm (HfCN film), zirconium carbonitride film (ZrCN film), molybdenumcarbonitride film (MoCN film), tungsten carbonitride film (WCN film) andthe like, metal carbide films such as a tantalum carbide film (TaCfilm), a hafnium carbide film (HfC film), zirconium carbide film (ZrCfilm), molybdenum carbide film (MoC film), tungsten carbide film (WCfilm) and the like, and silicide films such as a TiSiC film, a TaSiCfilm, a HfSiC film, a ZrSiC film, a MoSiC film, a WSiC film and the likewhich are formed by adding silicon (Si) to these metal carbide films.

Additional examples include, in case where the TaCN film is formed,TaCl₅ or TaF₅ used as the first raw material, Hf[C₅H₄(CH₃)]₂(CH₃)₂ usedas the second raw material and NH₃ used as the nitridation raw material.In addition, for example, in case where the HfCN film is formed, HfCl₄or HfF₄ is used as the first raw material, Hf[C₅H₄(CH₃)]₂(CH₃)₂ is usedas the second raw material and NH₃ is used as the nitridation rawmaterial. In addition, for example, in case where the ZrCN film isformed, ZrCl₄ or ZrF₄ is used as the first raw material,Hf[C₅H₄(CH₃)]₂(CH₃)₂ is used as the second raw material and NH₃ is usedas the nitridation raw material. In addition, for example, in case wherethe MoCN film is formed, MoCl₅ or MoF₅ is used as the first rawmaterial, Hf[C₅H₄(CH₃)]₂(CH₃)₂ is used as the second raw material andNH₃ is used as the nitridation raw material. In addition, for example,in case where the WCN film is formed, WCl₆ or WF₆ is used as the firstraw material, Hf[C₅H₄(CH₃)]₂(CH₃)₂ is used as the second raw materialand NH₃ is used as the nitridation raw material. In addition, thesecases may have the same film formation sequence and process conditionsas the first sequence of the above-described embodiment.

In addition, for example, in case where the TaC film is formed, TaCl₅ orTaF₅ is used as the first raw material and Hf[C₅H₄(CH₃)]₂(CH₃)₂ is usedas the second raw material. In addition, for example, in case where theHfC film is formed, HfCl₄ or HfF₄ is used as the first raw material andHf[C₅H₄(CH₃)]₂(CH₃)₂ is used as the second raw material. In addition,for example, in case where the ZrC film is formed, ZrCl₄ or ZrF₄ is usedas the first raw material and Hf[C₅H₄(CH₃)]₂(CH₃)₂ is used as the secondraw material. In addition, for example, in case where the MoC film isformed, MoCl₅ or MoF₅ is used as the first raw material andHf[C₅H₄(CH₃)]₂(CH₃)₂ is used as the second raw material. In addition,for example, in case where the WC film is formed, WCl₆ or WF₆ is used asthe first raw material and Hf[C₅H₄(CH₃)]₂(CH₃)₂ is used as the secondraw material. In addition, these cases may have the same film formationsequence and process conditions as the second sequence of theabove-described embodiment.

In addition, in case where the TiSiC film, the TaSiC film, the HfSiCfilm, the ZrSiC film, the MoSiC film and the WSiC film are formed, filmformation sequences to form the TiSiC film, the TaSiC film, the HfSiCfilm, the ZrSiC film, the MoSiC film and the WSiC film may furtherinclude a process of supplying a raw material, which contains silicon,as the third raw material (silane raw material). Examples of the silaneraw material may include chlorosilanes such as monochlorosilane (SiH₃Cl,abbreviated as MCS), hexachlorosilane (Si₂Cl₆, abbreviated as HCDS),tetrachlorosilane, i.e., silicon tetrachloride (SiCl₄, abbreviated asSTC), trichlorosilane (SiHCl₃, abbreviated as TCS), dichlorosilane(SiH₂Cl₂, abbreviated as DCS) and the like, inorganic raw materials suchas trisilane (Si₃H₈, abbreviated as TS), disilane (Si₂H₆, abbreviated asDS), monosilane (SiH₄, abbreviated as MS) and the like, and organic rawmaterials such as aminosilanes, for example, tetrakisdimethylaminosilane(Si[N(CH₃)₂]₄, abbreviated as 4DMAS), trisdimethylaminosilane(Si[N(CH₃)₂]₄H, abbreviated as 3DMAS), bisdiethylaminosilane(Si[N(C₂H₅)₂]₂H₂, abbreviated as 2DEAS), bistertiarybutylaminosilane(SiH₂[NH(C₄H₉)]₂, abbreviated as BTBAS) and the like. In addition, thesecases may have the same process conditions as one or more of theabove-described embodiments.

In addition, although the example of alternately supplying the first rawmaterial and the second raw material to the wafers 200 in the processchamber 201 to form the TiCN layer or the TiC film has been described inthe above embodiments, the first raw material and the second rawmaterial may be simultaneously supplied to cause a CVD reaction. Thiscase may also have the same process conditions as the sequences of theabove-described embodiment. The simultaneous supply of the first rawmaterial and the second raw material to the wafers 200 in the processchamber 201 can also provide the same operation and effects as theabove-described embodiment. However, the alternate supply of the firstraw material and the second raw material as in the above embodiment,that is, the alternate supply of the first raw material and the secondraw material with purge in the process chamber 201 therebetween, cancause a proper reaction between the first raw material and the secondraw material under the condition of dominant surface reaction andincrease controllability of film thickness.

In addition, although the example of forming the films using the batchtype substrate processing apparatus to process a plurality of substratesat once has been described in the above embodiment, the presentdisclosure is not limited thereto but may be suitably applied to filmformation using a single type substrate processing apparatus to processa single substrate or several substrates at once.

In addition, the above embodiments, modifications and applications maybe used in proper combinations.

In addition, the present disclosure may be implemented by change ofprocess recipes of an existing substrate processing apparatus, forexample. The change of process recipes may include installing theprocess recipes of the present disclosure in the existing substrateprocessing apparatus via a telecommunication line or a recording mediumstoring the process recipes, and operating the existing substrateprocessing apparatus to change its process recipes into the processrecipes of one or more of the embodiments described.

EXAMPLES Example 1

An XPS analysis was performed on a TiCN film formed on a wafer accordingto the first sequence in the above embodiment. In this example, TiCl₄gas was used as the first raw material gas, Hf[C₅H₄(CH₃)]₂(CH₃)₂ gas wasused as the second raw material and NH₃ gas is used as the nitridationraw material to form the TiCN film according to the film formation flowof FIG. 8 and the gas supply timings of FIG. 9. That is, the wafer wascarried in the process chamber (wafer loading), the wafer was heatedunder the N₂ atmosphere (preheat), a TiCN film was formed by alternatelyperforming formation of a TiC layer by alternately performing supply ofthe TiCl₄ gas and the Hf[C₅H₄(CH₃)]₂(CH₃)₂ gas (metal carbide layerformation) and irradiation of the formed TiC layer with NH₃ (nitridationprocess), residual materials in the process chamber are exhausted (gasexhaustion), and the wafer with the TiCN film is carried out of theprocess chamber (wafer unload) and was subjected to the XPS analysis.Process conditions for each step at that time were set as follows. Inaddition, for reference, a TiN film was subjected to XPS analysis in thesame way.

<Step 1>

Internal temperature of process chamber: 350° C.

Internal pressure of process chamber: 600 Pa (5 Torr)

Flow rate of TiCl₄ gas: 300 sccm

Irradiation time of TiCl₄ gas: 0.2 second

<Step 2>

Internal temperature of process chamber: 350° C.

Internal pressure of process chamber: 600 Pa (5 Torr)

Flow rate of Hf[C₅H₄(CH₃)]₂(CH₃)₂ gas: 20 sccm

Irradiation time of Hf[C₅H₄(CH₃)]₂(CH₃)₂ gas: 0.1 second

<Step 3>

Internal temperature of process chamber: 350° C.

Internal pressure of process chamber: 600 Pa (5 Torr)

Flow rate of NH₃ gas: 500 sccm

Irradiation time of NH₃ gas: 5 to 20 seconds

FIGS. 10A to 10C are views illustrating results of measurement of an XPSspectrum according to this example, FIG. 10A showing a result ofmeasurement of a Ti2p spectrum, FIG. 10B showing a result of measurementof a N1s spectrum and FIG. 10C showing a result of measurement of a C1sspectrum. In FIGS. 10A to 10C, a vertical axis represents bonding energy[eV] and a vertical axis represent measured intensity [a.u.]. A symbol •(indicated by a solid line) represents a result of measurement of theTiCN film according to this example and a symbol A represents a resultof measurement of the TiN layer for reference.

It can be seen from the measurement result shown in FIG. 10A that a peakindicating the existence of Ti is detected for both of the TiCN filmaccording to this example and the TiN film for reference, which meansthat Ti is contained in these films. It can be seen from the measurementresult shown in FIG. 10B that a peak indicating the existence of N isdetected for both of the TiCN film according to this example and the TiNfilm for reference, which means that N is contained in these films. Itcan be seen from the measurement result shown in FIG. 10C that a peak isdetected near 282.0 eV in the TiCN film according to this example, whichmeans that Ti—C bonding exists in this film. It can be seen from theseresults that Ti, C and N are contained in the TiCN film according tothis example. Peaks near 284.8 eV, 286.5 eV, 289.0 eV detected from theTiCN film indicate the existence of C—C, C—H, C—O and C—O—O bondings,which are detected from organic matters adhered to the surface of theTiCN film. A peak near 285 eV detected from the TiN film does notindicate the existence of C in the film but is derived from acontaminant organic matter adhered to the surface of the TiN film.

Example 2

An XPS analysis was made on a TiC film formed on a wafer according tothe second sequence in the above embodiment. In this example, TiCl₄ gaswas used as the first raw material gas and Hf[C₅H₄(CH₃)]₂(CH₃)₂ gas wasused as the second raw material to form the TiC film according to thefilm formation flow of FIG. 11 and the gas supply timings of FIG. 12.That is, the wafer was carried in the process chamber (wafer loading),the wafer was heated under the N₂ atmosphere (preheat), a TiC film wasformed by alternately supplying the TiCl₄ gas and theHf[C₅H₄(CH₃)]₂(CH₃)₂ gas (metal carbide film formation), residualmaterials in the process chamber are exhausted (gas exhaustion), and thewafer with the TiC film is carried out of the process chamber (waferunload) and was subjected to the XPS analysis. Process conditions foreach step at that time were set as follows.

<Step 1>

Internal temperature of process chamber: 350° C.

Internal pressure of process chamber: 600 Pa (5 Torr)

Flow rate of TiCl₄ gas: 300 sccm

Irradiation time of TiCl₄ gas: 0.2 second

<Step 2>

Internal temperature of process chamber: 350° C.

Internal pressure of process chamber: 600 Pa (5 Torr)

Flow rate of Hf[C₅H₄(CH₃)]₂(CH₃)₂ gas: 20 sccm

Irradiation time of Hf[C₅H₄(CH₃)]₂(CH₃)₂ gas: 0.1 second

FIGS. 13A and 13B are a view illustrating results of measurement of anXPS spectrum according to this example, FIG. 13A showing a result ofmeasurement of a Ti2p spectrum and FIG. 13B showing a result ofmeasurement of a C1s spectrum. In FIGS. 13A and 13B, a vertical axisrepresents bonding energy [eV] and a vertical axis represent measuredintensity [a.u.].

It can be seen from the measurement result shown in FIG. 13A that a peakindicating the existence of Ti is detected for the TiC film according tothis example, which means that Ti is contained in the film. It can beseen from the measurement result shown in FIG. 13B that a peak isdetected near 282.0 eV in the TiC film according to this example, whichmeans that Ti—C bonding exists in this film. It can be seen from theseresults that Ti and C are contained in the TiC film according to thisexample. A peak near 284.8 eV detected from the TiC film indicates theexistence of C—C and C—H bondings which are derived from an organicmatter adhered to the surface of the TiC film.

Additional Aspects of Present Disclosure

Hereinafter, some aspects of the present disclosure will be additionallystated.

A first aspect of the present disclosure may provide a method ofmanufacturing a semiconductor device, including: alternately performing(i) a first step of alternately supplying a first raw materialcontaining a first metal element and a halogen element and a second rawmaterial containing a second metal element and carbon to a substrate bya first predetermined number of times, and (ii) a second step ofsupplying a nitridation raw material to the substrate, by a secondpredetermined number of times, wherein alternating the first and secondsteps forms a metal carbonitride film containing the first metal elementhaving a predetermined thickness on the substrate.

In some embodiments, the first metal element is a transition metalelement.

In some embodiments, the first metal element includes at least oneelement selected from a group consisting of titanium, tantalum, hafnium,zirconium, molybdenum and tungsten.

In some embodiments, the first metal element includes titanium.

In some embodiments, the halogen element includes chlorine or fluorine.

In some embodiments, the halogen element includes chlorine.

In some embodiments, the first raw material includes TiCl₄.

In some embodiments, the second metal element includes a transitionmetal element.

In some embodiments, the second metal element includes at least oneelement selected from a group consisting of titanium, tantalum, hafnium,zirconium, molybdenum and tungsten.

In some embodiments, the second metal element includes hafnium.

In some embodiments, the second raw material includes a methyl group.

In some embodiments, the second raw material includes a cyclopentadienylgroup.

In some embodiments, the second raw material includes an ethyl group.

In some embodiments, the second raw material includesHf[C₅H₄(CH₃)]₂(CH₃)₂.

In some embodiments, each of the first metal element and the secondmetal element is a transition metal element.

In some embodiments, each of the first metal element and the secondmetal element includes at least one element selected from a groupconsisting of titanium, tantalum, hafnium, zirconium, molybdenum andtungsten.

In some embodiments, the first metal element includes titanium and thesecond metal element includes hafnium.

In some embodiments, the first step of alternately supplying the firstraw material and the second raw material by the first predeterminednumber of times includes alternately performing the supply of the firstraw material and the supply of the second raw material by a plurality ofnumber of times.

In some embodiments, the step of forming the metal carbonitride filmincludes alternately performing the first step of alternately supplyingthe first raw material and the second raw material by the firstpredetermined number of times and the second step of supplying thenitridation raw material, by a plurality of number of times.

In some embodiments, the first step of alternately supplying the firstraw material and the second raw material by the first predeterminednumber of times includes forming a metal carbide layer containing thefirst metal element on the substrate, and the second step of supplyingthe nitridation raw material includes forming a metal carbonitride layercontaining the first metal element by nitriding the metal carbide layer.

In some embodiments, the first step of alternately supplying the firstraw material and the second raw material by the first predeterminednumber of times includes forming a metal carbide layer containing thefirst metal element on the substrate while discharging the halogenelement contained in the first raw material and the second metal elementcontained in the second raw material, as the form of gas, and the secondstep of supplying the nitridation raw material includes forming a metalcarbonitride layer containing the first metal element by nitrizing themetal carbide layer.

Another aspect of the present disclosure may provide a method ofmanufacturing a semiconductor device, including: alternately performing(i) a first step of alternately supplying a first raw materialcontaining a first metal element and a halogen element and a second rawmaterial containing a second metal element and carbon to a substrate bya first predetermined number of times to form a metal carbide layercontaining the first metal element on the substrate while dischargingthe halogen element contained in the first raw material and the secondmetal element contained in the second raw material, as a form of gas,and (ii) a second step of supplying a nitridation raw material to thesubstrate to nitride the metal carbide layer, by a second predeterminednumber of times, wherein alternating the first and second steps forms ametal carbonitride layer containing the first metal element having apredetermined thickness on the substrate.

In some embodiments, the first step of alternately supplying the firstraw material and the second raw material by the first predeterminednumber of times includes transforming and discharging the halogenelement contained in the first raw material and the second metal elementcontained in the second raw material, as a gaseous material.

In some embodiments, the first step of alternately supplying the firstraw material and the second raw material by the first predeterminednumber of times includes transforming and discharging the halogenelement contained in the first raw material and the second metal elementcontained in the second raw material, as a gaseous material containingthe halogen element, a gaseous material containing the second metalelement, and/or a gaseous material containing the halogen element andthe second metal element.

In some embodiments, the first step of alternately supplying the firstraw material and the second raw material by the first predeterminednumber of times includes generating and discharging the halogen elementcontained in the first raw material and the second metal elementcontained in the second raw material, as a gaseous material containingthe halogen element, a gaseous material containing the second metalelement, and/or a gaseous material containing the halogen element andthe second metal element.

Another aspect of the present disclosure provides a method of processinga substrate, including: alternately performing a first step of supplyinga first raw material containing a first metal element and a halogenelement and a second raw material containing a second metal element andcarbon to a substrate by the first predetermined number of times and asecond step of supplying a nitridation raw material to the substrate, bythe second predetermined number of times, wherein alternating the firstand second steps forms a metal carbonitride film containing the firstmetal element having a predetermined thickness on a substrate.

Another aspect of the present disclosure provides a substrate processingapparatus including: a process chamber configured to accommodate asubstrate; a first raw material supply system configured to supply afirst raw material containing a first metal element and a halogenelement to the substrate in the process chamber; a second raw materialsupply system configured to supply a second raw material containing asecond metal element and carbon to the substrate in the process chamber;a niridation raw material supply system configured to supply anitridation raw material to the substrate in the process chamber; and acontrol unit configured to control the first raw material supply system,the second raw material supply system and the nitridation raw materialsupply system so as to alternately perform (i) a first step ofalternately supplying the first raw material and the second raw materialto the substrate in the process chamber by the first predeterminednumber of times, and (ii) a second step of supplying the nitridation rawmaterial to the substrate in the process chamber, by the secondpredetermined number of times, wherein alternating the first and secondsteps forms a metal carbonitride film containing the first metal elementhaving a predetermined thickness on the substrate.

Another aspect of the present disclosure provides a program that causesa computer to perform a process including: alternately performing (i) afirst step of alternately supplying a first raw material containing afirst metal element and a halogen element and a second raw materialcontaining a second metal element and carbon to a substrate in a processchamber of a substrate processing apparatus by the first predeterminednumber of times, and (ii) a second step of supplying a nitridation rawmaterial to the substrate in the process chamber, by the secondpredetermined number of times, wherein alternating the first and secondsteps forms a metal carbonitride film containing the first metal elementhaving a predetermined thickness on the substrate.

Another aspect of the present disclosure provides a non-transitorycomputer-readable recording medium storing a program that causes acomputer to perform a process including: alternately performing (i) afirst step of alternately supplying a first raw material containing afirst metal element and a halogen element and a second raw materialcontaining a second metal element and carbon to a substrate in a processchamber of a substrate processing apparatus by the first predeterminednumber of times, and (ii) a second step of supplying a nitridation rawmaterial to the substrate in the process chamber, by the secondpredetermined number of times, wherein alternating the first and secondsteps forms a metal carbonitride film containing the first metal elementhaving a predetermined thickness on the substrate.

Another aspect of the present disclosure provides a method ofmanufacturing a semiconductor device, including: alternately performinga first step of supplying a first raw material containing a first metalelement and a halogen element to a substrate and a second step ofsupplying a second raw material containing a second metal element andcarbon to the substrate, by the predetermined number of times, whereinalternating the first and second steps forms a metal carbide filmcontaining the first metal element having a predetermined thickness onthe substrate.

Another aspect of the present disclosure provides a method ofmanufacturing a semiconductor device, including: alternately performinga first step of supplying a first raw material containing a first metalelement and a halogen element to a substrate and a second step ofsupplying a second raw material containing a second metal element andcarbon to the substrate, by the predetermined number of times, whereinalternating the first and second steps forms a metal carbide filmcontaining the first metal element having a predetermined thickness onthe substrate while discharging the halogen element contained in thefirst raw material and the second metal element contained in the secondraw material, as the form of gas.

Another aspect of the present disclosure provides a method of processinga substrate, including: alternately performing a first step of supplyinga first raw material containing a first metal element and a halogenelement to a substrate and a second step of supplying a second rawmaterial containing a second metal element and carbon to the substrate,by the predetermined number of times, wherein alternating the first andsecond steps forms a metal carbide film containing the first metalelement having a predetermined thickness on the substrate.

Another aspect of the present disclosure provides a substrate processingapparatus including: a process chamber configured to accommodate asubstrate; a first raw material supply system configured to supply afirst raw material containing a first metal element and a halogenelement to the substrate in the process chamber; a second raw materialsupply system configured to supply a second raw material containing asecond metal element and carbon to the substrate in the process chamber;and a control unit configured to control the first raw material supplysystem and the second raw material supply system to alternately performa step of supplying the first raw material to the substrate in theprocess chamber and a step of supplying the second raw material to thesubstrate in the process chamber, by the predetermined number of times,thereby forming a metal carbide film containing the first metal elementhaving a predetermined thickness on the substrate.

Another aspect of the present disclosure provides a program that causesa computer to perform a process including: alternately performing afirst step of supplying a first raw material containing a first metalelement and a halogen element to a substrate in a process chamber of asubstrate processing apparatus and a second step of supplying a secondraw material containing a second metal element and carbon to thesubstrate in the process chamber, by the predetermined number of times,wherein alternating the first and second steps forms a metal carbidefilm containing the first metal element having a predetermined thicknesson the substrate.

Another aspect of the present disclosure provides a non-transitorycomputer-readable recording medium storing a program to cause a computerto perform a process including: alternately performing a first step ofsupplying a first raw material containing a first metal element and ahalogen element to a substrate in a process chamber of a substrateprocessing apparatus and a second step of supplying a second rawmaterial containing a second metal element and carbon to the substratein the process chamber, by the predetermined number of times, whereinalternating the first and second steps forms a metal carbide filmcontaining the first metal element having a predetermined thickness onthe substrate.

According to the present disclosure in some embodiments, it is possibleto provide a semiconductor device manufacturing method, a substrateprocessing method, a substrate processing apparatus and a program whichare capable of forming a metal carbide film with good step coverage.

While certain embodiments have been described, these embodiments havebeen presented by way of example only, and are not intended to limit thescope of the disclosure. Indeed, the novel methods and apparatusesdescribed herein may be embodied in a variety of other forms;furthermore, various omissions, combinations, substitutions and changesin the form of the embodiments described herein may be made withoutdeparting from the spirit of the disclosure. The accompanying claims andtheir equivalents are intended to cover such forms or modifications aswould fall within the scope and spirit of the disclosure.

What is claimed is:
 1. A method of manufacturing a semiconductor device,comprising forming a film containing a first metal element and carbon ona substrate by performing one or more times a cycle including: (a)supplying a first raw material containing a halogen element and thefirst metal element including at least one selected from a groupconsisting of titanium, tantalum, hafnium, zirconium, molybdenum andtungsten to the substrate to form a first layer containing the firstmetal element and the halogen element; and (b) supplying a second rawmaterial containing carbon and a second metal element including at leastone selected from a group consisting of titanium, tantalum, hafnium,zirconium, molybdenum, tungsten and aluminum to the substrate to reactthe halogen element contained in the first layer and the second metalelement contained in the second raw material to be transformed into agaseous material and discharge the gaseous material, thereby forming asecond layer containing the first metal element and the carbon.
 2. Themethod of claim 1, wherein the first layer includes a discontinuouslayer containing the first metal element and the halogen element.
 3. Themethod of claim 1, wherein the first layer includes a continuous layercontaining the first metal element and the halogen element.
 4. Themethod of claim 1, wherein the first layer includes a layer composed ofa combination of at least one of a discontinuous layer containing thefirst metal element and the halogen element or a continuous layercontaining the first metal element and the halogen element.
 5. Themethod of claim 1, wherein the first layer includes a discontinuouschemical adsorption layer of the first raw material.
 6. The method ofclaim 1, wherein the first layer includes a continuous chemicaladsorption layer of the first raw material.
 7. The method of claim 1,wherein the halogen element includes chlorine or fluorine.
 8. The methodof claim 1, wherein the second raw material includes a methyl group. 9.The method of claim 1, wherein the second raw material includes acyclopentadienyl group.
 10. The method of claim 1, wherein the secondraw material includes an ethyl group.
 11. The method of claim 1, whereinthe first raw material includes at least one selected from a groupconsisting of TiCl₄, TiF₄, TaCl₅, TaF₅, HfCl₄, HfF₄, ZrCl₄, ZrF₄, MoCl₅,MoF₅, WCl₆ and WF₆, and wherein the second raw material includes atleast one selected from a group consisting of Hf[C₅H₄(CH₃)]₂(CH₃)₂,Zr[C₅H₄(CH₃)]₂(CH₃)₂, Hf[N(C₂H₅)(CH₃)]₄, Zr[N(C₂H₅)(CH₃)]₄,Hf[N(CH₃)₂]₄, Ti[N(CH₃)₂]₄ and Al(CH₃)₃.
 12. The method of claim 1,wherein the first metal element contained in the first layer and thecarbon contained in the second raw material are bonded, in the (b). 13.The method of claim 1, wherein the halogen element contained in thefirst layer and the second metal element contained in the second rawmaterial are transformed into at least one selected from a groupconsisting of a gaseous material containing the halogen element, agaseous material containing the second metal element and a gaseousmaterial containing the halogen element and the second metal element,and discharged, in the (b).
 14. The method of claim 1, wherein thehalogen element contained in the first layer and the second metalelement contained in the second raw material are reacted to produce atleast one selected from a group consisting of a gaseous materialcontaining the halogen element, a gaseous material containing the secondmetal element and a gaseous material containing the halogen element andthe second metal element to be discharged as a gas, in the (b).
 15. Themethod of claim 1, wherein the cycle further includes (c) supplying anitridation raw material to the substrate to nitride the second layer.16. The method of claim 15, wherein the (c) is performed under conditionwhere a nitridation reaction of the second layer is unsaturated.
 17. Themethod of claim 15, wherein the cycle includes: alternately performingone or more times a first process of alternately performing the (a) andthe (b) one or more times, and a second process of performing the (c).18. The method of claim 15, wherein the cycle includes: alternatelyperforming one or more times a first process of alternately performingthe (a) and the (b) more than once, and a second process of performingthe (c).
 19. The method of claim 15, wherein the film containing thefirst metal element and the carbon further contains nitrogen.
 20. Asubstrate processing apparatus comprising: a process chamber configuredto accommodate a substrate; a first raw material supply systemconfigured to supply a first raw material containing a halogen elementand a first metal element including at least one selected from a groupconsisting of titanium, tantalum, hafnium, zirconium, molybdenum andtungsten to the substrate in the process chamber; a second raw materialsupply system configured to supply a second raw material containingcarbon and a second metal element including at least one selected from agroup consisting of titanium, tantalum, hafnium, zirconium, molybdenum,tungsten and aluminum to the substrate in the process chamber; and acontrol unit configured to control the first raw material supply systemand the second raw material supply system so as to form a filmcontaining the first metal element and the carbon on the substrate byperforming one or more times a cycle including: (a) supplying the firstraw material to the substrate in the process chamber to form a firstlayer containing the first metal element and the halogen element; and(b) supplying the second raw material to the substrate in the processchamber to react the halogen element contained in the first layer andthe second metal element contained in the second raw material to betransformed into a gaseous material and discharge the gaseous material,thereby forming a second layer containing the first metal element andthe carbon
 21. A non-transitory computer-readable recording mediumstoring a program that causes a computer to perform a process comprisingforming a film containing a first metal element and carbon on asubstrate by performing one or more times a cycle including: (a)supplying a first raw material containing a halogen element and thefirst metal element including at least one selected from a groupconsisting of titanium, tantalum, hafnium, zirconium, molybdenum andtungsten to the substrate to form a first layer containing the firstmetal element and the halogen element; and (b) supplying a second rawmaterial containing carbon and a second metal element including at leastone selected from a group consisting of titanium, tantalum, hafnium,zirconium, molybdenum, tungsten and aluminum to the substrate to reactthe halogen element contained in the first layer and the second metalelement contained in the second raw material to be transformed into agaseous material and discharge the gaseous material, thereby forming asecond layer containing the first metal element and the carbon.